Process of treating ceramic material



April 17, 1934. .1. R. PARSONS PROCESS OF TREATING CERAMIC MATERIAL Filed July 13. 1931 :.2 La p4 FLOCCULA'HON INVENTOR JOSEPH IE. Bq/PSOA/S. BY ATTORN EY Patented Apr. 17, 1934 Q 4 UNITED STATES- PA .ENT" omc .rnocsssor TREATING CERAMIC MATERIAL Joseph R. Parsons, Chicago, 111., assignor to United States Gypsum Company, Chicago; 111., a corporation of Illinois Application July 13, 1931, Serial No. 550,317 15 Claims. (Cl. 225-156) This invention relates to the process of treatmust be allowed to dry after several pieces have. ing ceramic materials, and has reference more been formed before it can be again used. -It has particularly to a process. of the class described also been heretofore difficult to moldclay articles I in which clay bodies are defiocculated, a delayed in permanent metal molds from thin clay slips beflocculent is added, and the resulting clay slip is cause of the fact that the molded pieces could not 60 poured into molds to solidify under the action of be set up or stiifened sufiiciently to remove'the the delayed flocculating reagent. article from the mold. V

The clay particles in water suspension hold in An object of this invention, therefore, is to their immediate vicinity various positive ions, 9. provide a process of treating ceramic or clay slips 10 state of combination commonly called adsorption. in which a fiocculating agent is added to a de- 65 Each of these ions can be replaced by other posiflocculated slip so that a controlled delayed stifftive ions under suitable conditions, i. e. (1) The ening action takes place in the mold after pourpresence of an excess of the replacing ion, the ing. replacing action then being due to a mass action Another object of the invention is to provide a effect or (2) the presence along with the replacprocess of preparing light weight heat insulating 70 ing ion of an anion with which the ion being -reand sound absorbing ceramic tiles in which'foam placed will form an insoluble'or non-ionized salt. air cells are locked in the deflocculated ceramic The viscosity of a clay slip is greatly dependent mix by a controlled delayed flocculation. on which ions are'adsorbed by the clay particles, A further object of the invention is to provide the monovalent ions except H+ tending to keep a process of molding ceramic bodies in metal 75 the clay particles separated in which case the slip molds where setting or flocculation of the clay is said to be defiocculated and is comparatively slip is obtained by salt capable of delayed flocfiuid while the divalent, trivalent and hydrogen culation or coagulation of the clay; also to imions tend to cause the individual clay particles to prove ceramic processes and compositions in other cling together in aggregates and in this state the respects hereinafter specified and claimed. slip is said to be fiocculated and is comparatively Reference is to be had to the accompanying viscous. The quantity of electrolyte which must drawing forming a part of this specification, in'

' be added to furnish sufficient ions to bring about which 1 the desired effect is small, usually well under 1% i Fig. 1 is a graphical chart showing the effect 30 of the weight of dry clay present. This is parof different amounts of deflocculating agents upon 5 ticularly true with respect to the flocculation of the relative fluidity of the clay slip, and a deflocculated slip using either acids, which Fig. 2 isa graphical chart showing the flocculatfurnish H+ ions, or salts of dior tri-valent metals ing time of a clay slip depending upon the amount which give the ions of those metals. The of fiocculating agent used. A

5 amounts of electrolytes required for defioccula- In preparing a clay slip for molding, followtion and for flocculation are not necessarily ing the process of my present invention, I mix a stoichiometrically equal. clay with water, and with a small quantity of when the clay is deflocculated and is in a new, sodium silicate, sodium carbonate, sodium hytral or alkaline condition, the clay particles range droxide or other soluble salts which have a deinsizebetween 0.1-micr s and 1.0 millimicronsin flooculating efiect. The resulting deflocculated size, and move independently of each other ,so clay slip should have aconsistency so that the that they cannot be. seen under the ordinary slip may be readily poured into the mold and fill microscope. The flocculated clay is ina coaguall of the recesses in the mold with the sharpest lated form and the massing or grouping of the detail. A deflocculating agent which I prefer to 45 particles into clusters can be seen under the use is black liquor or waste cellulose liquor o-bmicroscope. The fiocculated clay appears to ,tainedc-as a lay-product of the soda process in the I be dense and the particles collect in loose agglompaper industry. This black liquor is alkaline in erations, these groups acting to hold water in their natureand contains ligneous bodies which serve voids. as a bonding agent for the claywhen dry, and

50 Inthe molding of ceramic'wares,it has been the also contains about 50% water.'- Fig. 1 of the Practice 170 P a ay lip into a plaster mold, drawing shows the effect on the relative fluidity of the mold serving to withdraw the water from the the clay slip by the addition of various amounts slip until the material is stiff enough to handle. of black liquor thereto.

7 After a prolonged period in the mold, the piece It should be understood that various kinds 0 55 is withdrawn from the mold and the plaster mold clays can be used for molding clay articles, but

a characteristic formula to produce a white ware body is shown below? After preparing the deflocculated clay slip, the fiocculating agent can be added in an amount varying from 0.25% to 0.5% of the clay content. By varying the amount of fiocculating agent added to the clay slip, the flocculating time can be varied from 2 minutes to 2 hours as seen in Fig. 2 of the drawing. The fiocculating agent used for accomplishing the delayed flocculation, should be carefully selected to give the desired action. A substance which ionizes to give a fio'cculating ion (H+, Ca++, Mg++etc.) is to be used. Gypsum or calcined gypsum is the reagent recommended by me for this purpose, but other reagents which are moreor less satisfactory are barium sulphide,

calcium sulphide and zinc sulphate. The barium sulphide is preferably used in a concentration of 1.2% of the dry weight of the body and the calcium sulphideandzincsulphate are used in the ,proportions of 0.4% by weight of the dry body. The zinc sulphate has greater solubility than the other reagents mentioned and this higher solubility is somewhat overcome by introducing it in the form of coarser crystals. A crystalline zinc sulphate suitable for this purpose may have about the following screen a.nalysis:

'Ordinarily enough of the fiocculating agent is added tothe slip so that the flocculating time of the'slip is set for 10 to 15-minutes.

I After the fiocc'ulating agent has been added to the slip, the latter is immediately poured into the plaster, metal or other mold, the shape of the article to be cast, and in the time predetermined for flocculation, the slip stiffens up or coagulates sufficiently so thatthe piece can be removed from the mold; After removal from the casting or piece of ceramic ware is preferably allowed to air dry for a short time, and then is ,placeddn a dryer at a temperature somewhat below 212 F- After drying, the ceramic pieces are fired'for a period of 14 .to 16 hours at atemperature ranging from 2200 F. to 2300" F. -This firing temperature can be lowered somewhat by using a longer firingtime.

While my improved process involving deflocculation, followed by flocculation, is generally applicable to a variety of ceramic products, I have found it especially useful in the manufacture of an argilaceous or clay body is mixed with enough water to bring it to a thick slip. The alkaline mold, the

deflocculating agent previously described is now added to the thick clay slip, causing the slip to become defiocculated and thin in character with a low viscosity, but still containing comparatively little water. As shown in Fig. 1, the addition of a very small amount of deflocculating agent will cause a very great reduction in the viscosity or relative fiuidity of the slip. A stable foam is now prepared by beating a water solution of a foaming agent, such as soap bark; licorice root extract; casein, and rosin, together with a small amount of alkali. This stable foam is now thoroughly mixed with the defiocculated clay slip, and if desired, wood fiber can also be thoroughly mixed in. When mixing is complete, the fiocculating agent previously described is added and the mixing continues for a short period to insure thorough incorporation of the flocculating agent. The slip, still in a fluid form, is now poured into the mold, and within a fewminutes after pouring into the mold, the effect of the delayed fiocculating agent is felt and the slip stiffens up and becomes solid enough so that it may be removed from the mold. The article is now dried at room temperature, or may be dried at an elevated'temperature in a drying oven. The article is then put, into. the kiln and fired, so that the clay is hardeneii or vitrified and any fiber or other organic matter contained in the article is burned out. After burning, the casts or shapes are cooled, removed, and if the article is to be, used for acoustical absorption, the surface may be prepared by mechanically finis ing off the surface to open up the pores for the absorption of sound. The edges of the tiles may also be beveled to give a more pleasing architec- 1'10 tural effect. Pigments may be added to the mixture prior to flocculation, drying and burning, to produce any colored tile desired. Lacquers, enamels, paint, flake metal liquids, etc. may be applied to the acoustical surface if desired to 15 add to the-appearance, carebeing taken not to close up the pores relied upon to absorb the sound waves. 1 For every 2000 grams of thedry clay body,' about 1650 cc. of water are-necessary, but this water is varied, depending upon the exact character of the clay used. A preferred foam solution to use clay slip. The fine kaolin produces a foam which is. stabilized and does not break down. Other stabilizing agents may be used in the foam formula, such as gums, dextrins, etc.

For the wood fiber, I prefer a light, non-stain ing wood, such as bass wood, poplar, maple, etc. It is essential that the fiber does-not lose its strength when wet, but that it helps support the body and prevents excessive shrinkage in drying. It is quite possible to use a wide variety of sizes of fiber, but I prefer a fiber whose diameter is about maximum, and whose maximum length is about with a greater percentage of the fiber about A, in length, grading down to dust. I find it possible to use other types of fibrous, organic materials, which can be burned out on firing the tile. Granular organic' material, such as sawdust, may be used to replace a portion ofthe wood fiber and the foam. The space occupied by the fiber or organic matter, providescorridors or capillaries which connect up the cells provided by the foam, so that the sound can travel into the body of the material through these intercommunicating passages. The composition" is preferably molded so that the fibers extend substantially perpendicular to the face of the tile in order to obtain the maximum of sound absorbing efllciency. However, for tiles intended 'for'heat insulation, the composition is preferably molded in such a way that the fibers extend parallel to the face, so that the pores are not inter-communicating from the face of the tile inwardly, but constitute closed air spaces. x

A decorative glaze may also be applied to the surface of thebody prior to firing, care being taken in the manufacture of acoustical tile to prevent the glaze from closing up the larger surface pores. If the tile is not to be used for acoustical purposes, but only for heat insulation, the glaze may be such as to close all the surface pores and give a smooth, glossy surface.

As an example of my improved complete formula, the following is given:

The amount of re-agents to effect defiocculation and flocculation can readily be determined from the chart shown in Figs l and 2 depending somewhat on the type of clay used. It should be understood that the proportions shown in the above formula can be varied to a considerable extent, and other gas generating and density reducing re-agents may be used instead of a foam, such as aluminum powder and sodium hydroxide or black liquor, so as to produce the air cells in the finished body. Some clays occurin a naturally defiocculated'state so that a deflocculating agent will not be necessary for such clays.

I would state in conclusion that, while illustrated examples constitute a practical embodiment of my invention, I do not wish to limit myself precisely to these details, since manifestly, the same may be considerably varied without departing from the spirit of the invention as defined in the appended claims.

Having thus described my invention, I claim as new and desire to secure by Letters Patent:

1. A cellular plastic composition suitable for drying and firing to the point of vitrification, comprising clay, Water; foam, a deflocculating agent, and a fiocculating agent capable of coagulating the mixture after same has been formed into shape.

2. A ceramic composition comprising clay,

water, a deflocculating agent, a density reducing agent, and a fiocculating agent from the group consisting of calcium sulphate, barium sulphide, calcium sulphide, and zinc sulphate.

' 3. The process of preparing light weight material, which comprises mixing a defiocculated clay slip with foam, adding a fiocculating agent having a delayed fiocculating action, and drying and firing the fiocculated mixture to produce a porous material.

4. The process of preparing a porous material,

- which comprises mixing clay with less than its weight of water, deflocculating said clay by the addition of an electroiytesolution' to render the clay slip of high relative fluidity, mixing a density reducing agent with said defiocculated clay slip, adding a, fiocculating agent to the mixture to decrease the relative fluidity thereof, drying the mixture, and burning the dried mixture at a high temperature to the point of vitrification to produce a porous material.

5. The process of producing a cellular clay product. which comprises mixing clay with water,

adding to the mixture an alkaline-reacting sub- ,stance to effect defiocculation of said clay, incorporating a tenacious foam with the thus produced mixture, adding thereto a reagent capable of overcoming the defiocculation and causing a delayed fiocculating action so that when said flocculation occurs the foam-structure will be substantially retained and the bubbles of said foam entrapped, shaping the resultant mixture into form, drying said form, and-burning the same.

6. The process ofproducing a cellular clay product which comprises mixing clay with water,

adding alkaline black-liquor to the mixture to defiocculate the clay, adding a tenacious foam and incorporating the same throughout the mixture, adding thereto a fio'cculatingagent selected from the group consisting of gypsum, calcium sulfide, barium sulfide and zinc sulfate and pouring the resulting mixture into a mold to form the same, removing the form after the mixture has'set and entrapped the foam, drying the form, and burning the same to form the said vitrified product. K

v 7. The process of producing a cellular vitrified clay product which comprises preparing a mixture of clay-and water; adding a deflocculating agent thereto consisting of a material selected from the group consisting of black-liquor, sodium hydroxide, sodium carbonate and sodium -silicate; adding to the defiocculated mixture a tenacious foam made from water, soap-bark and kaolin and incorporating the foam uniformly through the mixture; adding a fiocculating agent consisting of hydrogen, barium, calcium and zinc; placing the resulting mixture rapidly into a mold and allowing it to setpup'therein; removing the molded object thus produced, drying the same, and then burning the same to vitrify it.

8. The process of producing a connectedlyporous and cellular-material of the ceramic type which comprises the steps of mixing clay with water; deflocculating the clay by addition of an alkaline-reacting substance thereto; forming a tenacious foam containing dispersed therein short .ligneous fibers; incorporating said foam with the defiocculated clay mixture; adding to the resulting mixture'a fiocculating agent having a relatively slow action; pouring the entiremixture rapidly into a mold to shape the same into predetermined form and allowing it to set up therein; removing the thus molded object and drying the same; and finally burning said object in a kiln whereby the ligneous fiber burns away forming intercohnecting channelabetween the individual cells of the foam-like structure of the product. I 1 I 9. The process of producing a porous cellular ceramic mass which comprises the steps of preparing a slip from clay and water; deflocculating the clay by adding to said slip an alkaline-react-- ing material selected from the group consisting of sodium hydroxide, sodiumv carbonate, sodium capable of yielding an ion selected from the group silicate, and black-liquor; adding aluminum POW-7 der to-the mixture to cause the liberation of a gas therein whereby the mixture is rendered of a foamy consistency; adding a flocculating reagent to the mixture to cause the same to setup and thus to trap the gaseous bubbles and to retain the fomaceous structure of the mixture; and subsequently drying the mixture and burning the 'same to form the ceramic mass.

10. The process of producing a cellular ce-' ramic product which comprises the steps of forming a mixture of clay and water; adding thereto an'alkaline-reacting deflocculating agent to deflocculatethe clay so'as to reduce the viscosity of the clay-water mixture; converting said mixture into a foamy mass by the introduction of a gaseous density-reducing agent thereinto; adding to the thus formed foamy mass a. reagent from the group consisting of gypsum, calcium' sulfide, barium sulfide and zinc sulfate to cause retarded flocculation of the mass to cause the .same to set up and thus to entrap the gaseous density-reducing agent and to preserve the foam-.

- like structure of the mass; and subsequently drying and burning said mass. 4

11. The process of producing a connectedly porous cellular burnt ceramic mass which comprises the steps of adding toa deflocculated claywater mixture a foam made from a solution of I said tile.

soap-bark and wood-fiber, forming the resulting foamy mass into shape, fiocculating the clay to set. the foamy structure, drying the mass thus formed, and burning the same to vitrify the clay and to burn out the wood fiber whereby interconnected cellularity will be imparted to the mass by the destruction of the wood fiber thus connecting the individual cells of the foam-like structure of the mass.

12. A burnt ceramic product of foam-like structure, having the foam-like-arranged voids thereof interconnected by small passages to render the product porous as well as cellular.

13. A burnt ceramic product of foam-like structure, consisting of burnt clay, anda substance selected from the group consisting of barium sulfide, calcium sulfide and zinc sulfate.

14. A'burnt ceramic tile having sound-absorbing properties consisting a body of clay contain- I ing voids of foam-like formation and interconnecting pores therein extending substantially in a-plane at right-angles to the larger surfaces of 

